The present invention is directed to organic light emitting devices (OLEDs) comprised of emissive layers that contain an organic compound functioning as an emitter and a separate intersystem crossing (xe2x80x9cISCxe2x80x9d) entity which operates to enhance the efficiency of the emission.
II. A. General Background
Organic light emitting devices (OLEDs) are comprised of several organic layers in which one of the layers is comprised of an organic material that can be made to electroluminesce by applying a voltage across the device, C. W. Tang et al., Appl. Phys. Lett. 1987, 51, 913. Certain OLEDs have been shown to have sufficient brightness, range of color and operating lifetimes for use as a practical alternative technology to LCD-based full color flat-panel displays (S. R. Forrest, P. E. Burrows and M. E. Thompson, Laser Focus World, February 1995). Since many of the thin organic films used in such devices are transparent in the visible spectral region, they allow for the realization of a completely new type of display pixel in which red (R), green (G), and blue (B) emitting OLEDs are placed in a vertically stacked geometry to provide a simple fabrication process, a small R-G-B pixel size, and a large fill factor, International Patent Application No. PCT/US95/15790.
A transparent OLED (TOLED), which represents a significant step toward realizing high resolution, independently addressable stacked R-G-B pixels, was reported in International Patent Application No. PCT/US97/02681 in which the TOLED had greater than 71% transparency when turned off and emitted light from both top and bottom device surfaces with high efficiency (approaching 1% quantum efficiency) when the device was turned on. The TOLED used transparent indium tin oxide (ITO) as the hole-injecting electrode and a Mg-Ag-ITO electrode layer for electron-injection. A device was disclosed in which the ITO side of the Mg-Ag-ITO layer was used as a hole-injecting contact for a second, different color-emitting OLED stacked on top of the TOLED. Each layer in the stacked OLED (SOLED) was independently addressable and emitted its own characteristic color. This colored emission could be transmitted through the adjacently stacked, transparent, independently addressable, organic layer or layers, the transparent contacts and the glass substrate, thus allowing the device to emit any color that could be produced by varying the relative output of the red and blue color-emitting layers.
PCT/US95/15790 application disclosed an integrated SOLED for which both intensity and color could be independently varied and controlled with external power supplies in a color tunable display device. The PCT/US95/15790 application, thus, illustrates a principle for achieving integrated, full color pixels that provide high image resolution, which is made possible by the compact pixel size. Furthermore, relatively low cost fabrication techniques, as compared with prior art methods, may be utilized for making such devices.
II.B. Background of Emission
II.B.1. Basics
II.B.1.a. Singlet and Triplet Excitons
Because light is generated in organic materials from the decay of molecular excited states or excitons, understanding their properties and interactions is crucial to the design of efficient light emitting devices currently of significant interest due to their potential uses in displays, lasers, and other illumination applications. For example, if the symmetry of an exciton is different from that of the ground state, then the radiative relaxation of the exciton is disallowed and luminescence will be slow and inefficient. Because the ground state is usually anti-symmetric under exchange of spins of electrons comprising the exciton, the decay of a symmetric exciton breaks symmetry. Such excitons are known as triplets, the term reflecting the degeneracy of the state. For every three triplet excitons that are formed by electrical excitation in an OLED, only one symmetric state (or singlet) exciton is created. (M. A. Baldo, D. F. O""Brien, M. E. Thompson and S. R. Forrest, Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Applied Physics Letters, 1999, 75, 4-6.) Luminescence from a symmetry-disallowed process is known as phosphorescence. Characteristically, phosphorescence may persist for up to several seconds after excitation due to the low probability of the transition. In contrast, fluorescence originates in the rapid decay of a singlet exciton. Since this process occurs between states of like symmetry, it may be very efficient.
Many organic materials exhibit fluorescence from singlet excitons. However, only a very few have been identified which are also capable of efficient room temperature phosphorescence from triplets. Thus, in most fluorescent dyes, the energy contained in the triplet states is wasted. However, if the triplet excited state is perturbed, for example, through spin-orbit coupling (typically introduced by the presence of a heavy metal atom), then efficient phosphoresence is more likely. In this case, the triplet exciton assumes some singlet character and it has a higher probability of radiative decay to the ground state. Indeed, phosphorescent dyes with these properties have demonstrated high efficiency electroluminescence.
Only a few organic materials have been identified which show efficient room temperature phosphorescence from triplets. In contrast, many fluorescent dyes are known (C. H. Chen, J. Shi. and C. W. Tang, xe2x80x9cRecent developments in molecular organic electroluminescent materials,xe2x80x9d Macromolecular Symposia. 1997, 125, 1-48; U. Brackmann, Lambdachrome Laser Dyes (Lambda Physik, Gottingen, 1997) and fluorescent efficiencies in solution approaching 100% are not uncommon. (C. H. Chen, 1997. op. cit.) Fluorescence is also not affected by triplet-triplet annihilation, which degrades phosphorescent emission at high excitation densities. (M. A. Baldo, et al., xe2x80x9cHigh efficiency phosphorescent emission from organic electroluminescent devices,xe2x80x9d Nature, 1998, 395, 151-154; M. A. Baldo, M. E. Thompson, and S. R. Forrest, xe2x80x9cAn analytic model of triplet-triplet annihilation in electrophosphorescent devices,xe2x80x9d 1999). Consequently, fluorescent materials are suited to many electroluminescent applications, particularly passive matrix displays.
II.B.1.b. Overview of Invention Relative to Basics
This invention pertains to the use of intersystem crossing agents to enhance emission efficiency in organic light emitting devices. An intersystem crossing agent, or molecule, is one which can undergo intersystem crossing, which involves the transfer of population between states of different spin multiplicity. Lists of known intersystem crossing agents, or molecules, are given in A. Gilbert and J. Baggott, Essentials of Molecular Photochemistry, Blackwells Scientific, 1991.
In one embodiment of the present invention, we focus on a way to use an intersystem crossing agent to increase efficiency in a system with a fluorescent emitter. Therein, we describe a technique whereby triplets formed in the host material are not wasted, but instead are transferred to the singlet excited state of a fluorescent dye. In this way, all excited states are employed and the overall efficiency of fluorescence increased by a factor of four. In this embodiment, the ISC agent traps the energy of excitons and transfers the energy to the fluorescent emitter by a Fxc3x6rster energy transfer. The energy transfer process desired is:
3D*+1Axe2x86x921D+1A*xe2x80x83xe2x80x83(Eq.1)
Here, D and A represent a donor molecule and a fluorescent acceptor, respectively. The superscripts 3 and 1 denote the triplet and singlet states, respectively, and the asterisk indicates the excited state.
In a second embodiment of the present invention, we focus on a way to use an intersystem crossing agent to increase efficiency in a system with a phosphorescent emitter. Therein, we describe a technique whereby the ISC agent is responsible for converting all of the excitons from a host material into their triplet states and then transferring that excited state to the phosphorescent emitter. This would include the case wherein the ISC agent only traps singlet excitons on the host and host triplet excitons are transferred directly to the phosphorescent emitter (rather than going through the ISC agent.)
In this second embodiment wherein phosphorescent efficiency is enhanced, a phosphorescent emitter is combined with an intersystem crossing agent such that the following can occur:
xe2x80x831D*+1Xxe2x86x921D+1X*
1X*xe2x86x923X*
3X*+1Axe2x86x921X+3A*
3A*xe2x86x921A+hv
wherein D represents the donor (host), X represents the intersystem crossing agent, and A represents the acceptor (emissive molecule). Superscript 1 denotes singlet spin multiplicity; superscript 3 denotes triplet spin multiplicity and the asterisk denotes an excited state.
In a third embodiment of the present invention, we focus on a way to use an intersystem crossing agent to increase efficiency by acting as a filter and a converter. In one aspect of the filter/converter embodiment, the intersystem crossing agent acts to convert singlet excitons to triplet excitons, thereby keeping singlets from reaching the emissive region and thus enhancing optical purity (the xe2x80x9cfilterxe2x80x9d aspect: singlets are removed and thus no singlets emit) and increasing efficiency (the xe2x80x9cconversionxe2x80x9d aspect: singlets are converting to triplets, which do emit).
These embodiments are discussed in more detail in the examples below. However the embodiments may operate by different mechanisms. Without limiting the scope of the invention, we discuss the different mechanisms.
II.B.1.c. Dexter and Fxc3x6rster Mechanisms
To understand the different embodiments of this invention it is useful to discuss the underlying mechanistic theory of energy transfer. There are two mechanisms commonly discussed for the transfer of energy to an acceptor molecule. In the first mechanism of Dexter transport (D. L. Dexter, xe2x80x9cA theory of sensitized luminescence in solids,xe2x80x9d J. Chem. Phys., 1953, 21, 836-850), the exciton may hop directly from one molecule to the next. This is a short-range process dependent on the overlap of molecular orbitals of neighboring molecules. It also preserves the symmetry of the donor and acceptor pair (E. Wigner and E. W. Wittmer, Uber die Struktur der zweiatomigen Molekelspektren nach der Quantenmechanik, Zeitschrift fur Physik, 1928, 51, 859-886; M. Klessinger and J. Michl, Excited states and photochemistry of organic molecules (VCH Publishers, New York, 1995). Thus, the energy transfer of Eq. (1) is not possible via Dexter mechanism. In the second mechanism of Fxc3x6rster transfer ( T. Fxc3x6rster, Zwischenmolekulare Energiewanderung and Fluoreszenz, Annalen der Physik, 1948, 2, 55-75; T. Fxc3x6rster, Fluoreszenz organischer Verbindugen (Vandenhoek and Ruprecht, Gottinghen, 1951 ), the energy transfer of Eq. (1) is possible. In Fxc3x6rster transfer, similar to a transmitter and an antenna, dipoles on the donor and acceptor molecules couple and energy may be transferred. Dipoles are generated from allowed transitions in both donor and acceptor molecules. This typically restricts the Fxc3x6rster mechanism to transfers between singlet states.
However, in one embodiment of the present invention, we consider the case where the transition on the donor (3D*xe2x86x921D) is allowed, i.e. the donor is a phosphorescent molecule. As discussed earlier, the probability of this transition is low because of symmetry differences between the excited triplet and ground state singlet.
Nevertheless, as long as the phosphor can emit light due to some perturbation of the state such as due to spin-orbit coupling introduced by a heavy metal atom, it may participate as the donor in Fxc3x6rster transfer. The efficiency of the process is determined by the luminescent efficiency of the phosphor (F Wilkinson, in Advances in Photochemistry (eds. W. A. Noyes, G. Hammond, and J. N. Pitts, pp. 241-268, John Wiley and Sons, New York, 1964), i.e. if a radiative transition is more probable than a non-radiative decay, then energy transfer will be efficient. Such triplet-singlet transfers were predicted by Fxc3x6rster (T. Fxc3x6rster, xe2x80x9cTransfer mechanisms of electronic excitation,xe2x80x9d Discussions of the Faraday Society, 1959, 27, 7-17) and confirmed by Ermolaev and Sveshnikova (V. L. Ermolaev and E. B. Sveshnikova, xe2x80x9cInductive-resonance transfer of energy from aromatic molecules in the triplet state,xe2x80x9d Doklady Akademii Nauk SSSR, 1963, 149, 1295-1298), who detected the energy transfer using a range of phosphorescent donors and fluorescent acceptors in rigid media at 77K or 90K. Large transfer distances are observed; for example, with triphenylamine as the donor and chrysoidine as the acceptor, the interaction range is 52 xc3x85.
The remaining condition for Fxc3x6rster transfer is that the absorption spectrum should overlap the emission spectrum of the donor assuming the energy levels between the excited and ground state molecular pair are in resonance. In Example 1 of this application, we use the green phosphor fac tris(2-phenylpyridine)iridium (Ir(ppy)3; M. A. Baldo, et al., Appi. Phys. Lett., 1999, 75, 4-6) and the red fluorescent dye [2-methyl-6[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-ylidene]propane-dinitrile] (xe2x80x9cDCM2xe2x80x9d; C. W. Tang, S. A. VanSlyke, and C. H. Chen, xe2x80x9cElectroluminescence of doped organic films,xe2x80x9d J. Appl. Phys., 1989, 65, 3610-3616). DCM2 absorbs in the green, and, depending on the local polarization field (V. Bulovic, et al., xe2x80x9cBright, saturated, red-to-yellow organic light-emitting devices based on polarization-induced spectral shifts,xe2x80x9d Chem. Phys. Lett., 1998, 287, 455-460), it emits at wavelengths between xcex=570 nm and xcex=650 nm.
It is possible to implement Fxc3x6rster energy transfer from a triplet state by doping a fluorescent guest into a phosphorescent host material. Unfortunately, such systems are affected by competitive energy transfer mechanisms that degrade the overall efficiency. In particular, the close proximity of the host and guest increase the likelihood of Dexter transfer between the host to the guest triplets. Once excitons reach the guest triplet state. they are effectively lost since these fluorescent dyes typically exhibit extremely inefficient phosphorescence.
Another approach is to dope both the phosphorescent donor and the fluorescent acceptor into a host material. The energy can then cascade from the host, through the phosphor sensitizing molecule and into the fluorescent dye following the equations (collectively Eq. 2):
3D*+1Xxe2x86x921D+3X*
3X*+1Axe2x86x921X+1A*
1A*xe2x86x921A+hvxe2x80x83xe2x80x83(2a)
xe2x80x831D*+1Xxe2x86x921D+1X*
1X*xe2x86x923X*
3X*+1Axe2x86x921X+1A*
1A*xe2x86x921A+hvxe2x80x83xe2x80x83(2b)
wherein X represents the sensitizer molecule and hv is the photon energy.
The multiple state energy transfer required in the phosphorescent-sensitized system is schematically described in FIG. 1. Dexter transfers are indicated by dotted arrows, and Fxc3x6rster transfers by solid arrows. Transfers resulting in a loss in efficiency are marked with a cross. In addition to the energy transfer paths shown in the figure, direct electron-hole recombination is possible on the phosphorescent and fluorescent dopants as well as the host. Triplet exciton formation after charge recombination on the fluorescent dye is another potential loss mechanism.
To maximize the transfer of host triplets to fluorescent dye singlets, it is desirable to maximize Dexter transfer into the triplet state of the phosphor while also minimizing transfer into the triplet state of the fluorescent dye. Since the Dexter mechanism transfers energy between neighboring molecules, reducing the concentration of the fluorescent dye decreases the probability of triplet-triplet transfer to the dye. On the other hand, long range Fxc3x6rster transfer to the singlet state is unaffected. In contrast, transfer into the triplet state of the phosphor is necessary to harness host triplets, and may be improved by increasing the concentration of the phosphor. To demonstrate the multiple state transfer, we used 4,4xe2x80x2-N,Nxe2x80x2-dicarbazole-biphenyl (xe2x80x9cCBPxe2x80x9d) as the host (D. F. O""Brien, M. A. Baldo, M. E. Thompson, and S. R. Forrest, xe2x80x9cImproved energy transfer in electrophosphorescent devices.xe2x80x9d Appl. Phys. Lett., 1999, 74, 442-444), Ir(ppy)3 as the phosphorescent sensitizer and DCM2 as the fluorescent dye. The doping concentration was 10% for Ir(ppy)3and 1% for DCM2.
The details, given in Example 1 below, showed the improvement in efficiency of fluorescent yield brought about by the use of the phosphorescent sensitizer. In the following sections, we give additional background.
II.B.2. Interrelation of Device Structure and Emission
Devices whose structure is based upon the use of layers of organic optoelectronic materials generally rely on a common mechanism leading to optical emission. Typically, this mechanism is based upon the radiative recombination of a trapped charge. Specifically, OLEDs are comprised of at least two thin organic layers separating the anode and cathode of the device. The material of one of these layers is specifically chosen based on the material""s ability to transport holes, a xe2x80x9chole transporting layerxe2x80x9d (HTL), and the material of the other layer is specifically selected according to its ability to transport electrons, an xe2x80x9celectron transporting layerxe2x80x9d (ETL). With such a construction, the device can be viewed as a diode with a forward bias when the potential applied to the anode is higher than the potential applied to the cathode. Under these bias conditions, the anode injects holes (positive charge carriers) into the hole transporting layer, while the cathode injects electrons into the electron transporting layer. The portion of the luminescent medium adjacent to the anode thus forms a hole injecting and transporting zone while the portion of the luminescent medium adjacent to the cathode forms an electron injecting and transporting zone. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, a Frenkel exciton is formed. Recombination of this short-lived state may be visualized as an electron dropping from its conduction potential to a valence band, with relaxation occurring. under certain conditions, preferentially via a photoemissive mechanism. Under this view of the mechanism of operation of typical thin-layer organic devices, the electroluminescent layer comprises a luminescence zone receiving mobile charge carriers (electrons and holes) from each electrode.
As noted above, light emission from OLEDs is typically via fluorescence or phosphorescence. There are issues with the use of phosphorescence. It has been noted that phosphorescent efficiency can decrease rapidly at high current densities. It may be that long phosphorescent lifetimes cause saturation of emissive sites, and triplet-triplet annihilation may also produce efficiency losses. Another difference between fluorescence and phosphorescence is that energy transfer of triplets from a conductive host to a luminescent guest molecule is typically slower than that of singlets; the long range dipole-dipole coupling (Fxc3x6rster transfer) which dominates energy transfer of singlets is (theoretically) forbidden for triplets by the principle of spin symmetry conservation. Thus, for triplets, energy transfer typically occurs by diffusion of excitons to neighboring molecules (Dexter transfer); significant overlap of donor and acceptor excitonic wavefunctions is critical to energy transfer. Another issue is that triplet diffusion lengths are typically long (e.g.,  greater than 1400 xc3x85) compared with typical singlet diffusion lengths of about 200 xc3x85. Thus, if phosphorescent devices are to achieve their potential, device structures need to be optimized for triplet properties. In this invention, we exploit the property of long triplet diffusion lengths to improve external quantum efficiency.
Successful utilization of phosphorescence holds enormous promise for organic electroluminescent devices. For example, an advantage of phosphorescence is that all excitons (formed by the recombination of holes and electrons in an EL), which are (in part) triplet-based in phosphorescent devices, may participate in energy transfer and luminescence in certain electroluminescent materials. In contrast, only a small percentage of excitons in fluorescent devices, which are singlet-based, result in fluorescent luminescence.
An alternative is to use phosphorescence processes to improve the efficiency of fluorescence processes. Fluorescence is in principle 75% less efficient due the three times higher number of symmetric excited states. In one embodiment of the present invention. We overcome the problem by using a phosphorescent sensitizer molecule to excite a fluorescent material in a red-emitting OLED. The mechanism for energetic coupling between molecular species is a long-range, non-radiative energy transfer from the phosphor to the fluorescent dye. Using this technique, the internal efficiency of fluorescence can be as high as 100%, a result previously only possible with phosphorescence. As shown in Example 1, we employ it to nearly quadruple the efficiency of a fluorescent OLED.
II.C. Background of Materials
II.C.1. Basic Heterostructures
Because one typically has at least one electron transporting layer and at least one hole transporting layer, one has layers of different materials, forming a heterostructure. The materials that produce the electroluminescent emission may be the same materials that function either as the electron transporting layer or as the hole transporting layer. Such devices in which the electron transporting layer or the hole transporting layer also functions as the emissive layer are referred to as having a single heterostructure. Alternatively, the electroluminescent material may be present in a separate emissive layer between the hole transporting layer and the electron transporting layer in what is referred to as a double heterostructure. The separate emissive layer may contain the emissive molecule doped into a host or the emissive layer may consist essentially of the emissive molecule.
That is, in addition to emissive materials that are present as the predominant component in the charge carrier layer, that is, either in the hole transporting layer or in the electron transporting layer, and that function both as the charge carrier material as well as the emissive material. The emissive material may be present in relatively low concentrations as a dopant in the charge carrier layer. Whenever a dopant is present, the predominant material in the charge carrier layer may be referred to as a host compound or as a receiving compound. Materials that are present as host and dopant are selected so as to have a high level of energy transfer from the host to the dopant material. In addition, these materials need to be capable of producing acceptable electrical properties for the OLED. Furthermore, such host and dopant materials are preferably capable of being incorporated into the OLED using materials that can be readily incorporated into the OLED by using convenient fabrication techniques, in panicular, by using vacuum-deposition techniques.
II.C.2. Exciton Blocking Layer
The exciton blocking layer used in the devices of the present invention (and previously disclosed in U.S. application Ser. No. 09/154,044) substantially blocks the diffusion of excitons, thus substantially keeping the excitons within the emission layer to enhance device efficiency. The material of blocking layer of the present invention is characterized by an energy difference (xe2x80x9cband gapxe2x80x9d) between its lowest unoccupied molecular orbital (LUMO) and its highest occupied molecular orbital (HOMO) In accordance with the present invention, this band gap substantially prevents the diffusion of excitons through the blocking layer, yet has only a minimal effect on the turn-on voltage of a completed electroluminescent device. The band gap is thus preferably greater than the energy level of excitons produced in an emission layer, such that such excitons are not able to exist in the blocking layer. Specifically, the band gap of the blocking layer is at least as great as the difference in energy between the triplet state and the ground state of the host.
For a situation with a blocking layer between a hole-conducting host and the electron transporting layer (as is the case in Example 1, below), one seeks the following characteristics, which are listed in order of relative importance.
1. The difference in energy between the LUMO and HOMO of the blocking layer is greater than the difference in energy between the triplet and ground state singlet of the host material.
2. Triplets in the host material are not quenched by the blocking layer.
3. The ionization potential (IP) of the blocking layer is greater than the ionization potential of the host. (Meaning that holes are held in the host.)
4. The energy level of the LUMO of the blocking layer and the energy level of the LUMO of the host are sufficiently close in energy such that there is less than 50% change in the overall conductivity of the device.
5. The blocking layer is as thin as possible subject to having a thickness of the layer that is sufficient to effectively block the transport of excitons from the emissive layer into the adjacent layer.
That is, to block excitons and holes, the ionization potential of the blocking layer should be greater than that of the HTL, while the electron affinity of the blocking layer should be approximately equal to that of the ETL to allow for facile transport of electrons.
[For a situation in which the emissive (xe2x80x9cemittingxe2x80x9d) molecule is used without a hole transporting host, the above rules for selection of the blocking layer are modified by replacement of the word xe2x80x9chostxe2x80x9d by xe2x80x9cemitting molecule.xe2x80x9d]
For the complementary situation with a blocking layer between a electron-conducting host and the hole-transporting layer one seeks characteristics (listed in order of importance):
1. The difference in energy between the LUMO and HOMO of the blocking layer is greater than the difference in energy between the triplet and ground state singlet of the host material.
2. Triplets in the host material are not quenched by the blocking layer.
3. The energy of the LUMO of the blocking layer is greater than the energy of the LUMO of the (electron-transporting) host. (Meaning that electrons are held in the host.)
4. The ionization potential of the blocking layer and the ionization potential of the host are such that holes are readily injected from the blocker into the host and there is less than a 50% change in the overall conductivity of the device.
5. The blocking layer is as thin as possible subject to having a thickness of the layer that is sufficient to effectively block the transport of excitons from the emissive layer into the adjacent layer.
[For a situation in which the emissive (xe2x80x9cemittingxe2x80x9d) molecule is used without an electron transporting host the above rules for selection of the blocking layer are modified by replacement of the word xe2x80x9chostxe2x80x9d by xe2x80x9cemitting molecule.xe2x80x9d]
II.D. Color
As to colors, it is desirable for OLEDs to be fabricated using materials that provide electroluminescent emission in a relatively narrow band centered near selected spectral regions, which correspond to one of the three primary colors, red, green and blue so that they may be used as a colored layer in an OLED or SOLED. It is also desirable that such compounds be capable of being readily deposited as a thin layer using vacuum deposition techniques so that they may be readily incorporated into an OLED that is prepared entirely from vacuum-deposited organic materials.
U.S. Ser. No. 08/774,333, filed Dec. 23, 1996, is directed to OLEDs containing emitting compounds that produce a saturated red emission.
At the most general level, the present invention is directed to organic light emitting devices comprising an emissive layer wherein the emissive layer comprises an emissive molecule, with a host material (wherein the emissive molecule present as a dopant in said host material) which molecule is adapted to luminesce when a voltage is applied across a heterostructure, wherein the emissive molecule is selected from the group of phosphorescent or fluorescent organic molecules and wherein the device comprises a molecule which can function as an intersystem crossing agent (xe2x80x9cISC moleculexe2x80x9d) which improves the efficiency of the phosphorescence or fluorescence relative to the situation where the ISC molecule is absent. It is preferred that the emissive molecule and the intersystem crossing molecule be different and it is preferred that there be substantial spectral overlap between the emissive molecule and the intersystem crossing molecule.
In a first embodiment wherein fluorescent efficiency is enhanced, a fluorescent emitter is combined with a phosphorescent sensitizer, which operates as an intersystem crossing agent. The phosphorescent sensitizer may be selected from materials wherein the radiative recombination rate is much greater than the non-radiative rate of recombination. The phosphorescent sensitizer may be selected from the group of cyclometallated organometallic compounds. The metal thereof may be selected from metals of the third row of the periodic table (especially W, Pt, Au, Ir, Os) and any other metals or metal compounds that have strong spin orbit coupling. The phosphorescent sensitizer may be further selected from the group of phosphorescent organometallic iridium or osmium complexes and may be still further selected from the group of phosphorescent cyclometallated iridium or osmium complexes. A specific example of the sensitizer molecule is fac tris(2-phenylpyridine)iridium, denoted (Ir(ppy)3) of formula 
[In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.]
A specific example of the fluorescent emitter is DCM2, of formula 
In a second embodiment of the present invention, wherein phosphorescent efficiency is enhanced, a phosphorescent emitter is combined with an intersystem crossing agent such that the following can occur:
1D*+1Xxe2x86x921D+1X*
1X*xe2x86x923X*
3X*+1Axe2x86x921X+3A*
3A*xe2x86x921A+hv
wherein D represents the donor (host), X represents the intersystem crossing agent, and A represents the acceptor (emissive molecule). Superscript 1 denotes singlet spin multiplicity; superscript 3 denotes triplet spin multiplicity and the asterisk denotes an excited state.
In a third embodiment of the present invention, a thin layer of an ISC agent is placed in the device; it may be between the HTL and ETL. The ISC agent is selected such that the optical absorption spectrum of the ISC agent overlaps strongly with the emission line of the material found at the site of recombination.
The general arrangement of the heterostructure of the devices is such that the layers are ordered hole transporting layer, emissive layer, and electron transporting layer. For a hole conducting emissive layer, one may have an exciton blocking layer between the emissive layer and the electron transporting layer. For an electron conducting emissive layer, one may have an exciton blocking layer between the emissive layer and the hole transporting layer. The emissive layer may be equal to the hole transporting layer (in which case the exciton blocking layer is near or at the anode) or to the electron transporting layer (in which case the exciton blocking layer is near or at the cathode).
The emissive layer may be formed with a host material in which the emissive molecule resides as a guest. The host material may be a hole-transporting matrix selected from the group of substituted tri-aryl amines. An example of a host material is 4,4xe2x80x2-N,Nxe2x80x2-dicarbazole-biphenyl (CBP), which has the formula 
The emissive layer may also contain a polarization molecule, present as a dopant in said host material and having a dipole moment, that affects the wavelength of light emitted when said emissive dopant molecule luminesces.
A layer formed of an electron transporting material is used to transport electrons into the emissive layer comprising the emissive molecule and the optional host material. The electron transport material may be an electron-transporting matrix selected from the group of metal quinoxolates, oxidazoles and triazoles. An example of an electron transport material is tris-(8-hydroxyquinoline)aluminum (Alq3).
A layer formed of a hole transporting material is used to transport holes into the emissive layer comprising the emissive molecule and the optional host material. An example of a hole transporting material is 4,4xe2x80x2-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl [xe2x80x9cxcex1-NPDxe2x80x9d].
The use of an exciton blocking layer (xe2x80x9cbarrier layerxe2x80x9d) to confine excitons within the luminescent layer (xe2x80x9cluminescent zonesxe2x80x9d) is greatly preferred. For a hole-transporting host, the blocking layer may be placed between the luminescent layer and the electron transport layer. An example of a material for such a barrier layer is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (also called bathocuproine or BCP), which has the formula 